AU595477B2 - Method for treating lignocellulose materials to obtain cellulose - Google Patents

Description

I PCI0R GAIAT6W4 MICNDWALE dk) L A~V E INTELLEC-J EL4;,I~ P TBureau inte o L~ DEMANDE INTERNATIONALE PUBLIEE EN VERTU DU TR$&OG#AT1% EIMATAVRE DE BREVETS (PCT) (51) Classification internationale des brevets 3 Numeiro de publication internationale: WO 84/ 03527 D21C 3/00 Al (43) Date de publication internationale: 13 septembre 1984 (13.09.84) (21) Nurn~ro de la demnande interuiationale: PCT/FR84/00042 (81) Etats disignis: AT (brevet europ~en), AU, BE (brevet europ~en), BR, CF (brevet OAPI), CG (brevet OAPI), (22) Date de dip6t international: 29 f~vrier 1984 (29.02.84) CH(brevet europ~en), CMv (brevet GAPI), DE (brevet europ~en), DK, Fl, FR (brevet europ~en), GA (brevet GAP!), GB (brevet europ~en), JP, LU (brevet (31) Numniros des demnandes prioritaires: 83/03415 europ~en), MR (brevet OAPI), N L (brevet europ~en), 83/12845 NO, SE (brevet europ~en), SN (brevet OAPI), SU, 83/14060 TD (brevet GAPI), TG (brevet OAPI), US.

(32) Dates de priorite: 2 mars 1983 (02.03.83) 4 ao~t 1983 (04.08.83) Publiie 2 septembre 1983 (02.09.83) .4vec rapport de recherche internationale.

Ave reedclon oiie ila; Pays de priorite: FRA ervndcosodfcs SEC-iON 34(4)(z) ODIRECT!ON SEE FO LI Kepresentant commun: iNV~LLAU DELA BRU-j AUSTRALIAN 1 ML N1ERE, Patrick, Marie, Francois; 45. boulevard de 1I Montmorency, F-751 16 Paris 28SP18 PATENT Of ICE o A)Title: METHOD FOR TREATING LIGNOCELLL'LOSENMATERIALS TO OBTAIN CELLULOSE (54)Titre: PROCEDE DE TRAITEMENT DE MATIERES LIGNO-CELLULOSIQUE POUR L'OBTENTION DE

CELLULOSE.

(57) Abstract Prenaration of cellulose pulp by treating lignocellulose material such as wood, bagasse, etc. in solid phase after irn *ppegnation with a chemical reactant, the quantity of aqueous solution during such treatment being very much reduce?, ko~rm I to 3 times the weight of lignocellulose material, hence very much lower than that of other processe's. The cooking is a calwied out at atmospheric pressure or under low pressure conditions, and in the First case the impregnation solution cone tait a third substance, such ats a solvent having a high boiling point of the glycol type, with a fatty acid salt, etc. to optionally lower the melting point of alcal-ine or alcaline earth reactants under approximately 1900C. After cooking, a black liouor which is directly combustible is obtained by pressing.

(57) Abrigi Pr&Toaration de pdte cellulosique par traitement d'une mati~re lign o-ct llulosique comme du bois. de la bagasse, etc.

en phase solide apr~s impregnation avec un r~actif chimique, la quantit6 de solution acqueuse pendant ce traitement &tant tr~s r~duiie, die I d 3 fois le poids de Ia mati~re ligno-cellulosique. donc tr~s inf~rieure d celle d'autres proc~d&s La cuisson a lieu d pression atmosph~rique ou sous faible pression, et dans le permier cas la solution di'imprlcgnation contient un tiersI corps, comme un solvant de point di' buIlition lev type glycol, un sel d'acide gras. etc. pouvaunt abaisscr le point de f'usion des r~actifs alcalins ott alcalino-terreux au dessous de 1900C. environ. Par pressage, apr~s cuisson on obtient une liqueur noire directement combustible.

LThis~ ckxcutient 'onlta ins the amC YI~drude under Sect i 0 i 49 kind is correct for I igI.I In traditional processes used today in industry, wood is treated by chemical aqueous solutions such as alkaline or alkaline earth salts of sulphydric acid or sulphurous acid.

These techniques have the following disadvantages; duration of cooking of several hours, up to hours, considerable dilution of the aqueous solutions which represent 5 to 10 times the weight of wood used, and thus the necessity to have a considerable volume of water available and to use a great amount of energy for heating to the cooking temperature.

The black liquid subproduct must be evaporated so as to reach a concentration of the order of 50% of dry matter, allowing combustion and chemical products to be recovered, thus needing a considerable energy consumption considering the mass of water used.

High investment costs due to the volumes and the service pressure of the reactors.

Pollution of the atmosphere by gaseous sulphurated subproducts (dimethylsulfide, methylmercaptan) Pollution of the waters by liquid cooking waste.

Other processes which have not reached the industrial level consist in treating the wood by solvents of the alcohol, amine, aminoalcohol, sulfoxide type in an acid medium or in the presence of alkaline or earth alkaline bases.

These processes which have certain advantages with respect to the traditional processes, such as a higher cooking rate (30 minutes to 3 hours) and absence of pollution, are however difficult to justify economically, because of the excessively high comsumption of the solvent used and the price thereof.

This consumption is itself related partly to the volume of solvent used (2 to 6 times the weight of the wood).

An improvement for reducing the consumption of solvent consists in treating the wood shavings in a twin-screw mixing extruder with a minimum of solvent and caustic soda for example, so as to obtain however a pasty consistence.

In this improved process, although the loss of solvent is reduced it is however not neglible and the equipment to be

A.

used must be specially tuned so as to avoid in particular a premature cellulose fiber-black liquid separation in the body of the extruder, which would lead to blockages.

The process of the invention allows most of the above-mentioned disadvantages to be avoided by cooking the wood shavings at atmospheric pressure or at a very low pressure in the solid phase after impregnation with a chemical reactant.

Accordingly, the present invention provides a process for the pulping of raw lignocellulosic material which comprises the steps of: impregnating said raw lignocellulosic material in finely divided form at atmospheric pressure with an impregnating solution, said impregnating solution containing water, 2 to by weight of alkali metal hydroxide, alkali metal salt, alkaline earth metal hydroxide or alkaline earth metal salt, and 2 to 20% by weight of a solvent having a boiling point S" above 150 0 C, said solvent selected from the group consisting of 0.

diols, alkanolamines and sulfoxides, said impregnating being effected at a temperature of 80 to 100 0 C using a quantity of 30 impregnating solution such that the amount of said alkali metal hydroxide or salt or alkaline earth metal hydroxide or salt retained by said raw lignocellulosic material is at least 11.3% of the dry weight of said material, and that the amount of said solvent retained is sufficient to lower the melting point of said alkali metal hydroxide or salt or alkaline earth metal hydroxide or salt in the impregnated mass to a temperature between 150 and 180 0

C,

removing unabsorbed impregnating solution from the impregnated mass, and adjusting the weight of the solution 30 retained during impregnation to a value representing 1 to 3 i times the weight of the treated material, cooking a material consisting of the resulting adjusted impregnated solid mass at a temperature from 150 to 190 0 C for to 60 minutes in an exclusively externally heated closed reactor without exerting any mechanical disintegration action on the mass, and pressing the cooked product so as to extract therefrom the solubilized lignin in the form of a black liquor containing 4 out 50% dry material.

-2rE ___I1 -14 a- This solid phase cooking is the essential characteristic of the invention. It allows: only a small amount of water to be used: 1 to 3 times the weight of the wood.

A black liquor to be collected having a high dry material concentration and so directly combustible.

Atmospheric pollution by sulfurated derivitives to be avoided, since the chemical reactants used do not contain any sulphur.

The consequences of these characteristics of the invention are: a reduced investment cost by using less bulky 39..30 ^3 f1^ -2a- _61 apparatus for the same production, a reduction in the size of the apparatus for concentrating the black liquor, a reduced requirement for anti-pollution equipment: A lesser energy consumption related to the considerable reduction of the mass of water to be heated or evaporated.

Two cases are to be considered depending on whether the cooking takes place at atmospheric pressure or at a pressure of a few kilograms/cm 2 FIRST CASE: At atmospheric pressure, it is preferable to add to the liquor for impregnating the shavings a small amount of a solvent with high boiling point 150 0 C) or a fatty acid salt or any other chemical product for lowering to 1500 1800 the melting temperature of the alkaline or earth alkaline reactants S used.

a~ Ir I I 0..

S

I*

*0 0 In this case the process comprises the following phases: i. Impregnation It is particularly important for the success of the following phases.

The impregnating liquid is water to which is added a solvent such as glycol, diol, ethanolamine, in an amount of 2 to 20%, and alkaline chemical reactants such as sodium carbonate, hydroxide, sulphide, or polysulphide, or alkaline earth metals soluble in water in an amount from 2 to This impregnation preferably takes place at a temperature close to 100 0 C, so as to ensure that the impregnation liquor penetrates to the core.

A more thorough mechanical dispersion of the wood also improves the impregnation.

2. Draining. Drying The impregnated shavings are drained, then the solid mass is introduced into an oven where it moves by gravity, or by a mechanical means (for example transported on a metal belt moving inside the oven as a layer a few centimeters thick).

3 -3- -J I _rr The water vapor, possibly with small amounts of solvent, which is released from the impregnated wood mass is recycled to the impregnation phase.

The latent heat is recovered.

3. Reaction The wood shavings still containing solvent in a small amount and the chemical reagents, are then heated to 150-190°C, at atmospheric pressure for a variable time (15 to 30 minutes, for example).

The solvent which is released is recovered and recycled.

o. During this solid phase treatment, the lignin reacts with the alkaline reactants.

4. Cellulose fiber black liquor separation hr. t The shavings leaving the oven have added *thereto a minimum amount of water so as to obtain a paste.

This is made possible by the fact that the lignin has been transformed into a water soluble product during the preceding treatment, which makes shredding of the wood easy without an intensive mechanical action.

o This paste is pressed in a conventional apparatus of the screw press type.

The advantage of adding the minimum amount of water is to obtain a concentrated black liquid easier o to bring to the dry condition or which may be directly burned so as to recover the alkaline reactants.

Complete extraction of the solubilized lignin using water is obtained by successive pressing operations preferably recycling the extracted liquor each time to the preceding extraction stage.

1SAL--, Then, t e washed cellulose paste is treated W n 4 67 i. in accordance with conventional purifying and bleaching processes.

With respect to a conventional process, the advantages which may be expected from such a process are: savings in energy.

In fact, the amount of water used is small and recovery of the latent heat from the water vapor is easy in the phase for drying the wood after impregnation.

Another important element is the elimination of the phase for concentrating the black liquid.

Lower investment costs.

The main items are: the phase for treating the wood or the 15 volume of equipment is reduced because of solid phase treatment and because of the shorter reaction time.

Elimination of equipment for concentrating the black liquid.

considerable reduction of pollution, by suppressing the residual reaction water since the chemical treatment takes place in the solid phase, 0 0. 0 00 6000 .000.

.0 S00

S

0

SO

by controlling the gas effluents when passing through the reaction oven.

With respect to the solvent phase processes, o the advantage is the small amount of solvent used which eliminates losses.

By way of indication, the solvent to wood ratio is about 1/10 of that of a solvent phase process

EXAMPLES

Among the numerous salt, base and solvent mixtures which may be used for implementing the reaction, t hose described below will be preferably chosen/ wj <2-H ;r' r Diethanolamine B.P. 268°C Monoethanolamine B.P 172"C SGlycol B.P- 197oC SPropylene glycol 189°C .Butyglycol B.P. 192°C SSulphur B.P. 112°C Soda NaOH Potassium KOH Lime Ca(OH)2 Na and K sulphides and polysulphides Na and K carbonates Na and K salts N and K salts of fatty acids such as stearic, oleic, etc...

Example 1 An aqueous solution is formed with water 900 g glycol 100 g 20 sodium hydroxide 100 g 200g of wood shavings (reckoned as dry weight) i.e. 260 g raw, are introduced into the solution.

The whole is evacuated 3 or 4 times then S 25 heated to about 100C.

S* After cooling, the impregnated shavings are drained.

S 0* After draining the weight is 915 g.

The wood has therefore absorbed 655 g of 30 solution.

The mass of impregnated shavings is then heated in an oven to a temperature of 180°C for 45 minutes During the first 20 minutes, about 280 g of water are collected containing a small amount of glycol.

After 45 minutes and at the same temperature, 02o 7 the oven is partially evacuated and 110 g of liquid are collected containing about 50%o glycol.

The vacuum is broken and the mass of shavings still hot is fed into a receptacle with arm stirrer.

containing 100 g of water.

A paste is obtained from which can be extracted by pressing when hot a thick black liquor, about 120g, containing about 50% dry matter.

The remaining paste is treated 3 times according to the same technique while extracting each time a less concentrated black liquor.

In an industrial process, the successive filtrates could be recycled to the preceding washing stage so as to obtain finally only a concentrated black 15 liquor.

o, After the last filtering and drying operations, 120 g of a paste with 10% water are obtained, i.e. 108 S: g reckoned as dry matter.

The black liquor may be incinerated and leaves 20 a soda carbonate residue.

Example 2 A solution is formed containing water 900 g 25 soda 100 g Sodium sulphidel00 g (reckoned as Na2s) The successive operations ar- the same as in Example 1.

However, during the passage through the oven 30 a slight release of sulphurated products is observed.

These may be incinerated and absorbed in a soda or soda carbonate solution.

Finally 115 g of cellulose paste with l1Ob water are recovered.

SALA* The incinerated black liquor leaves a sodium rbonate and sulphide residue.

1 B ji~'Yu ,;*i-rrrr-rl~t~~l~-L--YiLI-YILYU~I+ C SECOND CASE: Under slight pressure.

In this case, during the impregnation stage, it is possible to work with aqueous solutions of alkaline or earth alkaline salts in the absence of heavy solvents.

However, undei these conditions, it has been discovered that cooking at 150-190°C is preferably carried out in a closed reactor where outside heating then develops an internal pressure of about 3 to 8 kg/cm 2 The preferred apparatus according to the invention for carrying out the cooking consists in a metal cylinder in which the impregnated and drained S' shavings are introduced.

15 The cylinder is closed and the heating carried out from the outside, while the horizontally placed cylinder rotates about its axis.

This process is fundamentally different from the one used in vertical cookers of the Escher-Wyss 20 type for example where the preimpregnated shavings are heated by directly supplying vapor inside the reactor, which results in diluting the reaction mass which, after cooking, then has a consistency similar to molasses.

"In the process of the invention, after cooking 25 in the above described cylinder, these shavings have kept a solid appearance, but have lost any mechanical solidity.

The subsequent treatment phase characteristic of the invention consists in rapid crushing requiring 30 a low mechanical energy which transforms the cooked shavings into elementary fibers.

These fibers are then pressed after possibly adding a minimum amount of water so as to extract a concentrated black liquor therefrom In the following examples, we also show that n a small amount of heavy solvent may be used with the W lsuiprising result of improving the properties of the C: r -i cellulose paste obtained.

EXAMPLES

1 230.3 g of poplar wood reckoned as dry material, in the form of shavings, are introduced into a solution containing 10% NaOH. They are kept therein for 4 hours at 80 0

C.

The shavings are drained on a strainer then weighed. The weight is 632 g, i.e. 401.7 g of solution retained.

These shavings are introduced into a cylinder which they fill almost completely. After closing, this latter is rotated in an enclosure heated to 170°C for 1 hour 30 minutes.

S 15 2 Same operation as for 1, but using a 10% NaOH, glycol solution.

SThe results obtained are summed up in the S; following table.

Ex.l Ex.2 20 glycol in solution 0 NaOH in solution 10 Duration at 80°C 4H 4H NaOH introduced/dry wood 45.8 45.8 Weight of impregnated wood 632g 63 0 g Heating at 170°C 1H30 1H30 Net yield 46.3 47.86 uncooked material 0.04 0.03 Permanganate Index 13. 2 12.4 Photovolt whiteness 40.5 43 30 It can be seen that the presence of glycol causes: an improvement in whiteness, a higher yield, a better delignified paste.

S/ t EXAMPLES from picea shavings Method of procedure: XMPE rm ie saig i i i i-r 193 g of shavings reckoned as dry material are introduced into a solution containing soda and possibly glycol.

Impregnation takes place at 95°C for different times.

The shavings are drained and introduced into an externally heated steel cylinder.

Heating time at 170°C: 1 hour After cooking, the shavings are finally crushed and the resuiting paste is pressed, which gives a concentrated black liquor.

The remaining paste is treated with water, again pressed and refined.

The following table sums up the results obtained.

*0 400* ft *0

S.

0 6 *e@ O0 0 uin* Impregnation at Time: 4H NaOH: 10 %glycol: 10 weight of wood impregnated 456 NaOH retained with respect to the wood22.6 Cooking: 1 H at 170°C Overall yield 52.41 Net yield 52.39 uncooked 0.02 Permanganate index 32.6 Photovolt whiteness 32 Impregnation at 4H 12.5 10 4H 10 0 47.01 46.99 0.02 26 32.5 464.5 20.5 48.51 48.50 0.01 33.9 30 4H 12.5 0 475.5 23.5 45.19 45.16 0.03 27.8 34

S

S

9 0* .5 9 .9 0 0O 9 9 15 Time 3H 3H 3H 3H NaOH 10 12.5 10 12.5 glycol 10 10 0 0 weight of the impregnated wood 447 461 465 467 20 NaOH retained with respect to the wood 19.2 21 19.9 23.9 Cooking: 1H at 170°C Overall yield 51.75 46.3 51.02 46.04 Net yield 50.89 46.28 50.61 46.01 uncooked 0.86 0.05 0.41 0.03 Permanganate index 33 25.4 34 25.5 Photovolt whiteness 31 35.5 30 32.5 As in the examples concerning poplar, it was discovered that the presence of glycol improves: the permanganate index the whiteness the yield.

The same process also allowed a half chemical paste to be obtained.

Example 230.3 g of poplar wood Leckoned as dry matter I~ q__ are treated with the same operating procedure as before but under the conditions given in the table below: Impregnation at glycol 6 6 0 NaOH 6 6 6 Time 1H 2H 4H of wood impregnated 551 575 603 1 of soda retained/ dry wood 11.3 14.3 14.6 Cooking at 170°C 4* Time 1H30 1H30 1H30 S 15 Overall yield 67.2 60.4 54.7 Net yield 59.84 51.11 uncooked material 0.58 :.64 Permanganate index 61.8 36.4 28 Photovolt whiteness 16.5 22 27.5 Another characteristic of the process is that other lignocellulose materials may be used; In this case, it was discovered that when working with very light and divided lignocellulose materials, other than wood, such as: bagasse, straw, alfa, etc..., this list not being limitative, the impregnation of these materials leads to a retention of a considerable liquid mass of the order of 5 to 10 times their dry a weight.

30 This would lead to the loss of one of the advantages of 'his technology, the saving in water and so in energy, since this water will subsequently be vaporized.

This difficulty may be overcome.

It has in fact been discovered that the procedure a I can be as follows: i 111 1; Id~L C I ~II i 13 1. Impregnation 2. Pressing 3. Cooking During the impregnation stage, in this case, more dilute chemical solutions must be used.

The pressing carried out with conventional screw press type means leaves a compact product with dry appearance containing from one to two times its weight in water with respect to the dry starting material used.

It has been discovered, surprisingly, that the cooking of this compact product in a horizontal cylindrical apparatus heated from the outsid gives in a short time (15 minutes to 60 minutes) 3ild at a 15 temperature from 150 to 180°C, a perfectly delignified very homogenous paste containing little uncooked matter.

The paper obtained is of a good quality and its low coloration makes bleaching easy.

The following examples illustrate the process: Example n° 1: 92 g of dry bagasse from Guadeloupe are immersed in a solution containing 6% NaOH and 6% glycol at for 1 hour.

25 The impregnated mass is drained. Its weight is then 848 g.

This mass is thoroughly pressed on a hand actuated screw plate.

S 30 After pressing, a compact cake', whose weight is 267 g, remains.

This is roughly divided and placed in the cooking apparatus.

The cooking is carried out at 170°C for minutes.

Example n° 2: Same as example n* 1 but the impregnation Ssolution contains 5% soda and 5% glycol.

\glycol.

riia~ rm~ I Example n 0 3: Same as for example n 0 2, but the impregnation temperature is 70 0

C.

The following table gives the results obtained:

S

0@*O @5 S S S S 555 5

S.

S

555 55 S S S S 555 5 SO S eS 55

S

5@55 S S 05 S @5 4 5 5 55 55..

5 5 55

S

55

S.

S

5.555.

S S 14 a- 1eiqht of dry bagasse .Example I 9 2 g.

Example 2 .Examnple 3 Impregnation Temperature Time NaOH Glycol Impregnated bagasse s o* C.

I1 H.

.6 .6 *848 g.

809 C.

I H.

5 836 g.

708 C.

I H.

822 g.

236 g.

Weight after pressing NaOH retained with respect to dry bagasse.

Cooking Temperature 267 g.

243 g.

17, 3 15,4 1700 *0 0e S *0 20 5

S

*5 S

S

*5 overall yield uncooked met Yield 30' *38,8 0,8 *38 1700 306 41 0,7 40,3 io 102 15,1 1 700 43,15 0,8 42,7 permanganate index 5,5 1'2,5

S

S. S

S

*5e5 58 *5 S S 0e 0***SS phot ovol1t whiteness 47 Physical properties of the .Exa~mple I Time of refining treatme~it 6@ Weight by square irnter 62 Break index- 2 Lenth of the breach 4570 Stretch at drawing 2,1 44 obtaihfied paper.

*Example 2 6' 62 3,8 6800 2,3 43 *Example 3.

6# 62 4, 2 7500 2,45

MW

Claims (7)

1. A process for the pulping of raw lignocellulosic material which comprises the steps of: impregnating said raw lignocellulosic material in finely divided form at atmospheric pressure with an impregnating solution, said impregnating solution containing water, 2 to by weight of alkali metal hydroxide, alkali metal salt, alkaline earth metal hydroxide or alkaline earth metal salt, and 2 to 20% by weight of a solvent having a boiling point above 150 0 C, said solvent selected from the group consisting of diols, alkanolamines and sulfoxides, said impregnating being effected at a temperature of 80 to 100 0 C using a quantity of impregnating solution such that the amount of said alkali metal hydroxide or salt or alkaline earth metal hydroxide or salt retained by said raw lignocellulosic material is at least 11.3% of the dry weight of said material, and that the amount of said solvent retained is sufficient to lower the melting point of said alkali metal hydroxide or salt or alkaline earth metal hydroxide or salt in the impregnated mass to a temperature 1. between 150 and 180 0 C, removing unabsorbed impregnating solution from the impregnated mass, and adjusting the weight of the solution retained during impregnation to a value representing 1 to 3 times the weight of the treated material, cooking a material consisting of the resulting adjusted S" impregnated solid mass at a temperature from 150 to 190 0 C for 15 to 60 minutes in an exclusively externally heated closed reactor without exerting any mechanical disintegration action on the mass, and .30 pressing the cooked product so as to extract therefrom S the solubilized lignin in the form of a black liquor containing about 50% dry material.

2. A process according to claim 1, wherein the cooking takes place in an autoclave at a pressure of 3 to 8 bars.

3. A process according to claim 1 or claim 2, wherein the weight of the solution retained during impregnation is brought to a value between 1 to 3 times the weight of the treated fj,-,,,material by following the impregnation by draining and drying _LI in a tunnel oven, before subjecting the impregnated material to the cooking.

4. A process according to any one of claims 1 to 3, applied to the treatment of light and divided ligno-cellulose materials, such as straw, bagasse and alia, in which the impregnation is followed by pressing so as to bring the weight of the solution retained to a value between 1 and 1.5 times the weight of the treated material. A process according to any one of claims 1 to 4, wherein the cooked product is subjected to a mechanical disintegration in the presence of a small amount of water and is pressed so as to extract a black liquor containing about 50% of dry material.

6. A process according to claim 1 substantially as herein described with reference to any one of the Examples. S. DATED: 18 January 1990 S PHILLIPS ORMONDE FITZPATRICU Attorneys for: a TAG PULP INDUSTRIES, S.A. S o9 9 o o i g o -16- 11FF- VM INTERNATIONAL SEARCH REPORT International Appolication No PCT/F R 4/00042 a C a.. S. 5 a a.. S. 0 eg a Ce.' E C ee a C a C 06 0 I. CLASSIFICATION OF SUBJECT MATrTER (if Goeal Iclassification symbol* apply, Indicate all) I According to Internetionial Patent Classification (IPC) or to bath Naetional Claseification and IPC Int. Cl. 3 D 21 C 3/00 Ii. FIELDS6 SEARCHED Minimum Documentation Searched'4 Clasiication System IClaseffication Symbols Int. CI. 3 D21 C Documentation Searched other then Minimum Documentation to the Extent that such Documents are Included In tne Filds Searched Mi. DOCUMENTS CONSIDERED TO BE RELEVANT" es~agary Citation of Document, 16 with Indication. where appropriate, of the relevant passase I I Relevant to Clam No. Is 5 X US. A. 4135967 FOGARASSY) 23 January 1979, see claim 1; figure 2. 1-4. 6 column 5. line 14; column 6. line 4 X FR. A. 2459326 DE LA BRUNIERE) 09 January 1981. see the whole 1-6 document; cited in the application X US. A. 4017642 0. ORTH Jr. et 12 April 1977. see figure 1; column 1-4. 6.8 3. line 27; column 6. line 45; examples IlI-ViI X EP, A. 0054015 (SIMMER!NG-GRAZ-PAUKER) 16 June 1982. see claim 7.3 1; page 8. Lines 25.28 X FR. A. 2300149 (VISCH-GHIM IKO-TEC FN OLOGITSCHFESKI INSTITUT- NIS) 03 September 1976. see claim 1 1.2. 8 X FR. A. 989191 (TRAITEMENT CHINIIQUE DES VEGETAUX) 23 May 195 1 1 see the whole document US. A. 3255071 (T.N.KLEINERT) 07 June 1966, see column 1, line 10, columrj 1-3. 5, 7-9 X US. A. 2874044 (H.F.J.WENZL) 17 February 1959. see the whole document 1-4, 7-9 A US, A, 1735013 (G.A.RICHTER) 12 November 1929. see the whole document 1.2.4-6 A FR. A. 1566663 (RAYONIER) 09 May 1969. see the whole document 1.2.4. 6 Specili categories of cited documents: Is later document published after the International filing date A' document defining the generai state of the art which Is not or priority date and not In conflict with tho application but considered to be of particular relevance cited to understand the principle or theory uniderlying the invention earlier document but published on or after the international "X document of particular relevance: the claimed invention filing data cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive sltp which 1a cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reaeon (as specified) cannot be considered to involve an inventive step when the document refarring to an oral disclosure. use, exhibition or document is combined with one or more other such docu- other means ments. such comblrntion being obvious to a person skilled document published prior to the International Miing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the international Search a Date of Mailing of this International Search Report 24 May 1984 (24.05 .84) 09 July 1984 (09.07.84) International Searching Authority I Signature of Authorized Officer European Patent Office Form PCTIISAMI (21stecond shoot) (October 1981) F .rn .r ANNEX'TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL APPLICATION NO. PCT/FR 84/00042 (SA 6653) This Annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 03/07/84 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search date member(s) date report US-A- 4135967 23/01/79 CH-A- 498244 31/10/7.0 DE-A- 2046944 15/04/7." FR-A- 2063171 09/07/.7 LU-A- 61717 18/0171.: GB-A- 1328674 30/08/73.: US-A- 3887426 03/06/"5 BE-A- 756225 01/03/'- CA-A- 977505 11/11/73 AT-A- 300544 15/062.2 CH-A- 512635 15/09/71 OA-A- 3488 30/03/71 SE-B- 387382 06/09/76 SE-A- 7504423 16/04/75 FR-A- 2459326 09/01/81 None US-A- 4017642 12/04/77 None EP-A- 0054015 16/06/82 AT-A,B 372425 10/1083., US-A- 4451331 29/05784" FR-A- 2300149 03/09/76 OA-A- 4992 30/11/80 FR-A- 989191 US-A- 2597430 FR-A- 986984 BE-A- 478384 US-A- 2539093 US-A- 3255071 None US-A- 2874044 None US-A- 1735013 None FR-A- 1566663 09/05/69 GB-A- 1217573 31/12/70 DE-A- 1767028 17/02/72 CA-A- 871041 For more details about this annex see Official Journal of the European Patent Office, No. 12/82 ~I I I i RAPPORT DE RECHERCHE INTERNATIONALE Demands Inlternationaole N- PCT/FR 84/00042 r. CLASSEMENT DE L'INVENTION (sl plusleurs symboles do classification sont appllcables. lee inoiquer tous) Salon [a classification Internationals des brevets, (CIS) ou A Ia fois selon Ia classification nationals at Is CIB CIS. 3 D 21 C 3/00 'a S*4 C C lee I Cs C CI a Ce ass 5. C.. C 5550 C C' b 5, 55 C C 5. Ce 55 .5 5 S

11. DOMAINES SUR LESQUELS LA RECHERCHE A PORTEg Documentation minimale consultdo 6 Systbmo do classification Symboles do ctassification CIS. 3P 21 C Documentation conauitdo autre que Ia documentation minimale clans la mesure 00) de tots documents font partie des domalnes sur tesquels la recherche a portd

111. DOCUMENTS CONSIDIERLS COMME PERTINENTS 1 Catdgorle sIIdentification des documents citt~s,1 6 avec indication, al n6cessaire, j N* des revendicatlons des passages petinents 17 1 ls~es Is X US, A, 4135967 FOGARASSY) 23 janvier 01979, voir revendication 1; figure 2, 1-4,6 colonne 5, ligne 14 colonne 6, ligne 4 SX FR, A, 2459326 DE LA ERUNIBRE) 9 janvier 1981, voir 1'ensemble du brevet 1-6 (cit6 dans la demande) X US, A, 4017642 ORTH Jr. et al.) 12 avril 1977, voir figure 1; colonne 31 1-4,6,8 Iligne 27 colonne 6, ligne a exemples II-ViI X EP, A, 0054015 (SIMMERING-GRAZ-PAUKER) 16 juin 1982, voir revendication 1; 1,5,7,8 page 8, lignes 25-28 X FR, A, 2300149 (vISCH CHIMIKO-TECHNOLOGIT- SCHESKI INSTITUT-NIS) 3 septembre 1976, voir revendication 1, 1,2,8 *Catdgorles spdcilas de documents citds: Is sy document d~finissant I'41t g~n~rat do 13i technique. non considhrd comma pafllculibromant pertinent sa document ant~rieur, mats publi4 A la date do d6p6t Interna- tional ou aprbs cotta data a L document pouvant leter i'n douto sur une revandication do prioritd ou cit6 pour d~terminer Is data do publication d'une autro citation ou pour una raison spdctale (tells qutlndiqude) ssdocument so r~fdrant A uno divulgatlon orate, A un usage, A Itnoo ep osition ou lous autras moyons sP* document publiI avant la date do d~p~t International, mals post6riourement A Ia date do prioritd revendiqu~s *Txa document uit~rleur pubtli postdrleuroment Ala data do d~pdt international ou A to data do priortA at n'appartanant pas A l'6tat do la technique pertinent, mais c6t6 pour compreridre to prIncIpe ou ao ttAorie constituent la bass do I'invention CX a document particuligrement pertinent: Pi'nvontion rovendi- qu~s no pout itre considdr~e comma nouvelle ou comma Impliquant une activitd Inventive a Y 2 d, uument particulibrement pertinent-, lInvention raven- diquE. no pout Etre considdrdo comma Imoiiquant un. activild inventive lorsque Ie document eat assocI6 A un ou plusieurs autres documents do m~mo nature, cotte combi- nation 6tant Evidente pour una personna du mdtier. an document qut fait partia do t. m~mo tarnilia do brevets IV. CERTIFICATION Date 6 laquello Ia recherche Internationale a M6A ofectivement Data d'eapdditlon du pr~sent rappor do 0 24 mai 1984 09. 07.84t Administration charge do Ia rechercho Internationale I Signature du fonctionnalro autorlsE.Iof OFFICE EUROPEEN DES BREVETS j .Lw Formulalre PCTIISA/210 (dauxtime feultle) (Octobre 1981) Demnande Internationale N, PCT/FR 84/00042 -2- (SUITE DES RENSEIGNEMENTS INCOUtS SUR LA Ill. DOCUMENTS CONSIOgRgS COMME PE.!TINENTS 14 DEUXItME FEU.LLE) Ctgr Identification des documn nts CitdS, avec Indication, st n~cessaire T N* des revendications Catgoiedes 1assages pertinents 'T I isies I X FR, A, 989191 (TRAITEMENT CHIMIQUE DES VEGETAUX) 23 rnai 1951, voir l1ensemble 1 du brevet X US, A, 32550l71 KLEINERT) 7 juiri 1966, voir colonne 1 ligne 10 colonne 3, I 1-3,5, ligne 11 exemple 2 7- X US, A, 2874044 WENZL) 17 f~vrier 1959, voir 1 'ensemble du brevet 1-4, I 7-9 A US, A, 1735013 RICHTER) 12 novernbre I *9 1929, voir 1'ensemble du brevet 1,2,4-6 A FR, A, 1566663 (PLAYONIER) 9 rnai 1969, voir 1'ensernble du brevet I 1,2,4,6 Formulaire~~~~ PCS 9 tuleadtinel)(cor 91 ANNEXE AUL PPORT DE RECH-ERCHE INTERNATIC .LE RELATIF A LA DEMANDE INTERNATIONALE NO. PCT/FR 84/00042--SA 6653) La presente annexe indique les membres de la ffarille de brevets relatiis aux documents brevets cites dans le rapport de recherche international vis6 ci-dessus. Lesdi,:s membres sont ceux contenus au fichier informatique de I Offfice europeeri brevets a la date du 03/07/84 Les renseignements fournis sont donn~s A titre indicatif et n'engagent pas la responsabilit6 de l'Office europ~en des brevets. Document brevet Date de Membre(s) de La Date de cit6 au rapport publication farnille de brevets oubLic-atio*.n de recherche 4135967 23/01/79 CHi-- 49 82 4 4/1/ D, DE-A 2046944 13/041/71 LU-A- 61717 13/01/71 GB-A- 13296741- 30/08/73 *0JS-A- 3887426 03/06/75 06BE-A- 756225 0103;/7, .CA-A- 977505 1, /7 AT-A- 3005S44 15/06/72 CHi-A- 512635 15/'09/71 OA-A- 3488 30/03/7:1 SE-B- 387382 06,/09/70- SE-- 5042316/ 04/75 Soo FR-A- 2459326 09/01/81 Aucun US-A- 4017642 12/04/77 Aucun Soo 1P-A- 00-54015 1-0/06/82 A- A,B 37-2 425S 10/1.0/83 US-A- 4451331 29 ,/05/34 0 .6OER-A- 2300149 03/09/76 OA-A- 41992 30/11/80 I-A- 989191 US-A- 21597430 ~FR-A- 986984 BE-A- 4I78384 US-A-- 2539093 US-A- 3255071 Aucun US-A- 28740441 Aucun US-A- 1735013 Aucun FR-A- 1566663 09/05/69 GB-A- 1217573 31 /12 DE-A- 1767028 17 G2 /7 2 CA-A- 871041 Pour tout renseignement concernant cette annexe: voir journal Offficiel de l'Office europ~en des brevets, No. 12,8S2